A chemical system is described for releasing a good yield of free barium neutral atoms and barium ions in the upper atmosphere and interplanetary space for the study of the geophysical properties of the medium. The barium is released in the vapor phase so that it can be ionized by solar radiation and also be excited to emit resonance radiation in the visible range. The ionized luminous cloud of barium becomes a visible indication of magnetic and electrical characteristics in space and allows determination of these properties over relatively large areas at a given time

Lewis, B. W.

Murphy, W. J.

Smith, E. W.

Stokes, C. S.

English

NASA Technical Reports Server

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ATTN OF: GP
NATIONAL AERONAUTICS AND SPACE ADMINISTRATION
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SEP 0 5 1973
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Attention: Miss Winnie M. Morgan
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ISt-i SUBJECT: Announcement of NASA-Owned U.S. Patents in STAR
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o£?l In accordance with the procedures agreed upon by Code GP
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forwarded for abstracting and announcement in NASA STAR.
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NOTE - If this patent covers an invention made by a corporate
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Enclosure
Copy of Patent cited above
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https://ntrs.nasa.gov/search.jsp?R=19730021365 2020-03-17T09:07:14+00:00Z
United States Patent
»
Paine et al.
[in 3,751,913
[45] Aug. 14, 1973
[ 54 ] BARIUM RELEASE SYSTEM
[76] Inventors: Thomas O. Paine, Administrator of
the National Aeronautics and Space
Administration with respect to an
invention of; Bevertey W. Lewis,
Hampton; Charles S. Stokes, Willow
Grove, both of Va.; Edward W.
Smith, Exton; William J. Murphy,
King of Prussia, both of Pa.
[22] Filed: July 31, 1970
[21] Appl. No.: 59,892
[52] U.S. Cl 60/215, 149/1, 149/36,
252/305, 252/301.4
[51 ] Int. Cl C06d 5/06
[58] Field of Search 60/211, 214, 215;
252/305, 301.4 R; 149/36, 1
[56] References Cited
UNITED STATES PATENTS
3,658,609 4/1972 Lum et al 149/36
Primary Examiner—Benjamin R. Padgett
Attorney—John R. Manning, Howard J. Osborn and
Wallace J. Nelson
[57] ABSTRACT
A chemical system for releasing a good yield of free
barium (Ba°) atoms and barium ions (Ba+) to create
ion clouds in the upper atmosphere and interplanetary
space for the study of the geophysical properties of the
medium.
2 Claims, 2 Drawing Figures
Patented Aug. 14, 1973 3,751,913
SATURATION LINE
100 %
N2H4
100 %
8o(N03)2
FIG. 2 [NVENTORS
8EVERLEY W. LEWIS
CHARLES S. STOKES
EDWARD W. SMITH
WILLIAM J. MURPHY
BY
ATTORNEYS
3,751,913
BARIUM RELEASE SYSTEM
ORIGIN OF THE DISCLOSURE
The invention described herein was made in the per-
formance of work under a NASA contract and is sub-
ject to the provisions of section 305 of the National
Aeronautics and Space Act of 1958, Public Law
85-568 (72 Slat. 435; 42 USC 2457).
This invention relates generally to a chemical release
A more complete appreciation of the invention and
many of the attendant advantages thereof will be
readily apparent as the same becomes better under-
stood by reference to the following detailed description
when considered in connection with the accompanying
drawings wherein:
FIG. 1 is a schematic representation of the fuel and
oxidizer tanks connected to an open-ended combustion
chamber in a launch rocket for release of barium ac-
system and relates in particular to a system for releas- 10 cording to the present invention; and
ing barium in the vapor phase so that it can be ionized
by solar radiation and also be excited to emit resonance
radiation in the visible range. The ionized luminous
cloud of barium then becomes a visible indication of
magnetic and electric characteristics in space and al-
lows determination of these properties over relatively
large areas of space at a given time compared to rocket
borne or orbiting instruments. For example, a geomag-
netic field line could be illuminated by the present in-
vention from pole-to-pole.
Presently, barium release systems are used to create
ion clouds in the upper atmosphere for the study of
geophysical properties of the atmosphere. These
known systems utilize a solid chemical system using a
thermite mixture of barium and copper oxide as the
heat-producing reaction and an excess of barium to be
vaporized. This system is launched by a suitable rocket
and, at a predetermined time, the ingredients are ig-
FIG. 2 is a plot of triangular coordinates which de-
fines the barium nitrate-barium chloride-hydrazine
mixtures of the present invention.
Referring now to the drawings and more particularly
15 to FIG. 1, there is shown a segment of a suitable carrier
vehicle 10, such for example a rocket motor. Vehicle
10 is employed to carry fuel tank 11, insulated oxidizer
tank 13 and combustion chamber 15, along with the
necessary instrumentation, from earth into the upper
20 atmosphere or into interplanetary space. Fuel tank 11
is in fluid connection with combustion chamber 15 and
oxidizer tank 13 is in fluid connection with combustion
chamber 15 by way of respective conduits 17 and 19.
A pair of valves 21 and 23 are disposed within the re-
25 spective conduits 17 and 19. Valves 21 and 23 are
adapted to be selectively and simultaneously opened by
a suitable battery-powered timing mechanism, radio
signal, or the like, to release the pressurized fuel and
. . . . . . . . . . oxidizer from tanks 11 and 13. The fuel and oxidizer
nited and released from a canister through a burst dia-
 30 then flow th h condujts ,7 an£, „ and jm .
phragm and nozzle. The resulting barium cloud gives a
 each Qther th h a central, positioned mani.
brilliant color that can be observed and studied from
 fo,d an(J suitab,e jets (not snown) in combustion cham.
earth to give indications of wind currents and the like.
 ber lg whefe spontaneous ignition occurs. The reac-
This known system of barium release has proved effec- ,ion products are then expelled through the open ends
live but is inherently of low efficiency in producing bar-
 35 of combustion chamber 15 as plasma which includes
ium vapor yielding, in practice, only from 2 to 4 per-
 the desired barium neutral atoms and barium ions as
individual species.
The fuel utilized in fuel tank 11 is either hydrazine
(NjH,) or liquid ammonia (NH3) while the oxidizer
into the canister and must be done under inert atmo- 40 employed is selected from the group consisting of liq-
spheric conditions which proves time-consuming and
 ujd fluorine (F2), chlorine trifluoride (CIF3) and oxy-
gen difluoride (OFS). When using hydrazine as the fuel,
barium may be dissolved therein as barium chloride,
Bad], or barium nitrate, Ba(NO3)2, or a combination
cent of the total chemical weight when actually up to
48 percent is available. In addition, the barium-copper
oxide mixture is a fire hazard when mixing and pressing
costly in operation. Also, little, if any, ionization takes
place in this known system due to the initial heat gener-
ating reaction.
It is therefore an object of the present invention to 45 of the two. When using liquid ammonia as the fuel, bar-
provide a new and novel barium release system for at- ium meta! may be <"s*>lved therein. The combination
mospheric and space studies. found to Prod"ce the highest intensity of Ba° and Ba+
resonance radiation in ground based tests involved a
Another object of the present invention is a system fuei of 16 percent Ba(NO3)2, 17 percent BaCl, and 67
for releasing barium in the vapor phase so that it can 50 percent N,H4; and as the oxidizer, the cryogenic liquid
be ionized by solar radiation and excited to emit reso- fluorine F2 and in which an oxidizer to fuel weight ratio
nance radiation in the visible range.
Another object of the present invention is a novel
chemical mixture for releasing a good yield of free
atoms and barium ions. 55
was 1.32.
Other combinations of ingredients tested are set forth
in Table I below:
TABLE I
SystemA further object of the present invention is a binaryliquid hypergolic chemical release system in which bar-
ium is formed as a vapor at the time of release.
The foregoing and other objects are attained in one 60 16.7 Bad«-
aspect of the present invention by providing a liquid ?6%!j Ii.H<
fuel, in which barium salts are dissolved, and a high en- *
ergy oxidizer which spontaneously ignites the fuel on
contact. The barium release is accomplished by im-
pinging fuel and oxidizer jets in an open-ended com- 65
buation chamber which expels the reaction product
gases or plasma and which includes the desired barium
neutral atoms (Ba°) and barium ions (Ba+) as individ-
ual species.
Optimum O/F Percent
Ionization
Calculated
74% N.HJCIF,
50% Ba(NO,),—50%NH,/C1F,
42.9% Ba(NO,),-
57.1% N.H./C1F,
16.7%BaCI,-
83.3% N.H./F,
26% BaCl,-
74% N.H4/F,
2l%BaCl,-
9% Ba(NO,),-
70% N.JVF,
2.36
2.08
1.52
1.19
1.95
1.71
1.57
68.0
70.0
50.0
68.8
70.6
68.5
3,751,913
l7%BaCU-
16% Ba(NO,),— 67% N,HJf,
13% BaCl,-
21.5% Ba(NO,),-
65.5% N.IVF,
9% BaCl,—
30% BafNO,),-
61% N.IVF,
42.9% Ba(NO,),-
57.1% N.H./F,
42.9 % Ba(NO,),—
57.1% N.H./OF,
26% BaCL,-
74% N,H,/OF,
1.31
1.34
1.04
0.976
0.694
1.22
68.1
63.7
63.7
43.0
46.9
52.8
The conditions under which each of the combinations
listed in Table I were tested were ambient and the per-
centage ionization was calculated by equations set
forth in NASA Contract Report CR-1415 published in
August 1969.
The chemical supplier and manufacturers stated pu-
rity for the various chemicals employed are set forth in
less than the stoichiometric O/F. The stoichiometric
O/F is defined as being equivalent to the oxidizer to
fuel weight ratio in a balanced equation assuming the
salt is converted to free Ba, F to HF, Cl to HC1 and O
5 to HjO. For example, one system tested had an O/F
ratio of 142 grams oxidizer per 100 grams fuel or
1.42/1.00. If the barium is assumed to be converted to
BaFj then the stoichiometric O/F is 1.47. Since the
greatest light output in all cases occurred with O/F less
10 than stoichiometric it is apparent that little of the Ba
was combined as BaF2 or BaCl2. This was confirmed by
spectrographic analysis.
In Table II the various systems are listed in decreas-
ing light output or relative light intensity as measured
15 by phototubes in millivolts, thereby indicating the rela-
tive barium yield.
TABLE III
Table II below:
TABLE II
Chemical
N.H,
NH,
BaCl,
Ba(NO,),
F,
C1F,
OF,
Supplier
Olin Mathieson Chemical
Company, Lake Charles,
Louisiana
Air Products and Chemicals
Allentown, Pa.
J.T. Baker & Co.
Phillipsburg, N.J.
J.T. Baker & Co.
Phillipsburg, N.J.
Air Products & Chemicals
Allentown, Pa.
Allied Chemical Co.
Baton Rouge, La.
Allied Chemical Co.
Baton Rouge. La.
Purity
Technical Grade
97-98% N,H«
(2-3% H,O)
Technical Grade
Reagent Grade
Reagent Grade
98%
99.5%
98%
2o SYSTEM
(percent weight for fuel)
17% BaCI2. 16% Ba(NO,)v 67% Nii JF,
13% Bad,- 21.5% Ba(NO,),- 65:5% N.H^F,
25 21%BaCl,-9%Ba(NOs),-70%
N.IVF,
9% BaCl,-30% Ba(NO3),-61% N.H^F,
26% BaCl,-74% N.H./F,
26% BaCl,-74% N.H./OF,
16.7% BaCl,-83.3% N.H./F,
42.9% Ba(NO,),-S7.1% N.HJF,
,n 42.9%Ba(NO3),-57.1% N,H4/OF,
ou
 42.9%Ba(NO,),-57.1%N,H^CIF3
50% Ba(NOa),-50% NHj/ClF,
Maximum Relative
Intensity, millivolts
Ba° Ba*
5535 A. 4554 A.
27600 11800
23600 8340
20600 9100
16600 5970
16600 6520
11800 2100
9100 3350
9000 1 800
7300 1330
663 94
221 44
From the above information, it is readily seen that
35 the 17 percent BaQz- 16 percent Ba(NO3)z-67 percent
A solubility study of various mixtures containing Ba(-
NOa)i, BaClj and N2H4 was made at room temperature
and is shown in the triangular plot of FIG. 2. Seven so-
lutions that were used in the tests enumerated in Table
I are indicated by reference letters in FIG. 2 as follows:
a. 16.7 percent BaCl2 - 83.3 percent N2H4
b. 26 percent BaCI2 - 74 percent N2H4
c. 21 percent BaClj- 9 percent Ba(NO3)2 - 70
percent N,H4
d. 17 percent BaCl2 - 16 percent Ba(NO3)2 - 67
percent N2H4
e. 13 percent BaClz-21.5 percent Ba(NO3)2-65.5
percent NZH«
f. 9 percent Bad, - 30 percent Ba(NO3)2 - 61
percent N2 H4
g. 42.9 percent Ba(NO3)2 - 57.1 percent N2H4
A mixture below the Saturation Line, that is toward
the Ba(NO3)s or BaClj corners contained a solid and a
solution phase whereas the salts were in complete solu-
tion above the saturation line.
All fuel mixtures or systems described were easily
handled except the 50 percent BafNOj^SO percent
NH3 system. This system caused clogging of the feed
valves due to precipitation of the Ba(NO3)2. In addition
the light values obtained using this system was rela-
tively low.
In testing of each of the fuel mixtures set forth in
Table I the Ba° light was greater than the Ba+ light for
a given oxidizer/fuel ratio in each of the mixtures. The
maximum light occurred in all systems at a point lo-
cated between the stoichiometric O/F and 3 percent
N2H4/FZ system gave the greatest amount of light inten-
sity of the 4,554 A Ba+ and 5,535 A Ba° spectral lines.
Ambient tests showed that the optimum oxidizer to fuel
ratio of this system was 1.32 to 1.00. This system con-
40 taining 8.52 weight percent barium was estimated to be
68.1 percent ionized. Also since this system had the
largest relative light intensity it would be expected to
give the greatest amount of Ba° and Ba+ and would ap-
pear to be the optimum system for a barium payload.
45 In all systems tested it was found that the relative light
reached a maximum at the O/F corresponding to the
stoichiometric equation yielding barium as one of the
reaction products and that the relative light output was
sensitive to the O/F. Moving to either side of the opti-
50 mum O/F caused a sharp decrease in relative light.
In vacuum tests the ignition of each system tested was
smooth and like the ambient tests, took place in the
combustion chamber. The rapid expansion in vacuum
caused a decreased atom and ion density in the lumi-
cc nous flame which caused the light intensity to be about
one thirty-seventh to one-fiftieth the intensity mea-
sured in ambient tests. The percentage ionization was
approximately the same for vacuum and ambient tests.
The operation of the invention is now believed appar-
60 ent. Initially, fuel tank 11 is charged with the fuel con-
taining-the desired quantity of dissolved barium salt
and pressurized with helium. The fuel tank pressure
may be in the range of 6.89 to 20.06 x 105
Newton/meter*. Oxidizer tank 13 is also charged with
65 the appropriate oxidizer and pressurized. Cryogenic
oxidizers such as OF2 and F2 are condensed from gases
in the closed oxidizer tank which must be maintained
enclosed in a liquid nitrogen bath. The oxidizer feed
3/751,913
valve 23 and conduit 19 must also be maintained at liq-
uid nitrogen temperature with a liquid nitrogen jacket
when employing a cryogenic oxidizer.
The noncryogenic oxidizer, C1F3) may be pressurized
into the closed oxidizer tank 13 from a supply bottle
with super dry nitrogen.
Combustion chamber IS is formed of stainless steel,
aluminum, or the like Fj compatible metals and is inter-
nally partitioned by the manifold, not shown. The con-
duits 17 and 19 terminate in a manifold having injector
orifices (not shown) mounted 90° to each other within
each end of chamber 15 and sized for pressure drops
of 5.24 to 10.2 X 105 Newton/meter2 across the orifice.
10
ducing barium clouds wherein the degree of ionization
in the released plasma is much greater. The selectively
opening and closing of valves 21 and 23 gives the possi-
bility of a payload with multiple releases permitted due
to the start and stop capabilities of the liquid system.
Also, the liquid system of the present invention gives
the possibility of controlling rates so that a trail-type
release can be obtained as well as a point-source type.
In addition, the liquid system of the present invention
effects the formation of barium atoms and ions at the
time of combustion and expansion at high temperatures
and results in little opportunity for the barium to con-
dense during release.
There are obviously many variations and modifica-Fuel and oxidizer flows are in the range of 2.05 to 6.82
Kg/sec each. The entire system is carried into the upper \ 5 tions to the present invention that will be readily appar-
atmosphere or interplanetary space by rocket vehicle ent to those skilled in the art without departing from
10 where, in response to a suitable signal, timing mech- the spirit or scope of the disclosure or from the scope
anism or the like, valves 21 and 23 may be selectively of the claims.
opened and closed and the pressurized liquid fuel and What is claimed as new and desired to be secured by
oxidizer will flow through conduits 17 and 19 into com- 20 Letters Patent of the United States is:
bination unit 15. When the hypergolic liquids impinge 1. A method of releasing a good yield of free barium
upon each other, they spontaneously ignite to expel re-
action product gases or plasma including the highly lu-
minous barium neutral atoms and barium ions as indi-
vidual species. All of the barium reaching the combus- 25
tion chamber is vaporized and released through the op-
posite ends thereof so that a high yield efficiency is ob-
tained. The resulting high flame temperature, approxi-
mately 4,000° K., and some as yet not determined
chemical activation, produces a relatively large amount 30
of barium ions in the flame which is a highly desirable
condition. It has been estimated from spectroscopic
measurements that the degree of ionization may be as
high as 75 percent in the released plasma in compari-
son to being on the order of 1 percent for the previ- 35
ously used Ba-CuO solid system which depends almost
entirely on solar photoionization, a time-dependent
phenomena which further reduces the usable barium
yield of this known system.
Thus, it is readily apparent that the present invention 40
provides an inherently more efficient process of pro-
atoms and barium ions in a gaseous medium comprising
the steps of:
dissolving a barium salt selected from the group con-
sisting of BaCl2, Ba(NO3)2 and a mixture of BaCl,
and Ba(NO3)2 in a liquid fuel selected from the
group consisting of hydrazine and liquid ammonia,
providing a liquid oxidizer selected from the group
consisting of OFS, F2 and C1F2 for the fuel,
releasing the liquid fuel containing the barium salt
simultaneously with releasing the liquid oxidizer so
that the two released liquids contact each other
whereby a hypergolic reaction takes place to re-
lease a high yield of luminous barium atoms and
barium ions in the resulting flame.
2. The method of claim 1 wherein the liquid fuel
comprises:
a fuel mixture consisting of 67 percent N2H«, 17
percent BaCl2 and 16 percent Ba(NO3)2, by weight,
and the oxidizer is a fluorine oxidizer.
45
50
55
60
65


Barium release system

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